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The Crystal Structure of Wroewolfeite, a Mineral with Lcu+(OH)E(SO4XH2O)L Sheets

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The Crystal Structure of Wroewolfeite, a Mineral with Lcu+(OH)E(SO4XH2O)L Sheets American Mineralogist, Volume 70, pages 1050-1055, 1985 The crystal structureof wroewolfeite,a mineral with lCu+(OH)e(SO4XH2O)lsheets F. C. H,C.WTHORNEAND L. A. GNOET Departmentof Earth Sciences,Uniuersity of Manitoba Winnipeg,Manitoba, Canqda, R3T 2N2 Abstract The crystal structure of wroewolfeite,Cun(SOa[OH)6'2H2O, monoclinic, a : 6.0a5(1), b : 5.646(1),c : A.337Q)A,B :93.39(l)', / : 488.5(1)A3,space group Pc, has beensolved by direct methods and refined by full-matrix least-squaresto an R index of 6.7% usingTll observed(I > 2.5o\ reflections measuredon a twinned crystal. The fundamental building block of the wroewolfeitestructure is a [Cun(SOnXOH)rr]t- hetropolyhedralcluster that polymerizesin two dimensionsby edge-sharingbetween octahedra to form the structure module, a [Cu4(SO4[OH)6(H2O)]' sheet that is parallel to {001}. These sheetsare linked solely by hydrogenbonding, involving an additional (HrO) anion that is not directly bonded to a cation. This [Cu4(SO4XOH)6(H2O)]'sheet is also found in posnjakite and may also occur in langite.This and other related sheetsmay be describedby the generalformula [MoX,d.-.], in which M : octahedrallycoordinated cation, X : complex anion, @: simple anion (e.g' O'z-, (OH)-, (HrO)").Thefollowing structures are included: n : 0, botallackite;n : 1,wroe- wolfeite,langite, posnjakite; n :2, ktenasite,serpierite, devillite. The intra-module linkages and hydration states in these minerals may be interpreted in terms of the Lewis ba- sicity/acidityof structural fragments. Introduction tube and a highly oriented graphite crystal monochromalor mounted with equatorial geometry. A random orientation photo- Wroewolfeiteis a monoclinic hydrated copper hydroxyl graph showed many of the reflections to occur as pairs with an sulphateCun(SOn[OH)6.2H2O, first describedby Dunn intensity ratio of -3: 1. Twenty-five reflections were centered, and and Rouse (1975) from the Loudville lead mine, the correct unit cell was selected from an array of real space Loudville, Massachusetts.They assignedit to the same vectors corresponding to potential unit cell axes. Twenty-three of group as posnjakite,Cun(SOn[OH)u.HrO, and langite, the twenty-five reflections had integral indices; the rernaining re- Cuo(SOo[OH)6'2H2O,and it is presumablydimorphous flections were discarded as being from an alternate twin compo- with langite. nent. Additional reflections were centered and indexed, until the twenty-five reflections were all from the same twin component. Least-squares refinement of these reflections produced the mono- Experimental clinically constrained cell dimensions given in Table I, together Thematerial used in thisstudy is from theLoudville lead mine, with the orientation matrix relating the crystal axes to the diffrac- Loudville, Massachusetts, and was obtained from the Department tometer axes. of Mineralogy and Geology, Royal Ontario Museum, collection Intensity data were collected in the 0-20 scan mode, using 96 - number M37058. Single-crystal X-ray precession photographs in- steps with a scan range from [20(MoKdt) 1]' to f20(MoKar) dicate monoclinic symmetry, with systematic absences ld)l; * 1]" and a variable scan rate between 4.O and 29.3'lmin depend- l:2n + 1, consistent with space groups P2/c and Pc. The ob- ing on the intensity of an initial one second count at the center of served cell dimensions are in good agreement with the values the scan range. Backgrounds were measured for half the scan time reported by Dunn and Rouse (1975). The crystals are twinned by at the beginning and end of each scan. Two standard reflections reflection on {001}, leading to overlap on reflections of the type were monitored every 48 measurements to check for stability and 4h'k'1. This overlap is not merohedral; there is a distinct misre- constancy of crystal alignment. A total of 2588 reflections were gistry of the reflections. This twinlaw was reported by Dunn and measured over two asymmetric units out to a maximum 20 of 55". Rouse (1975). However, there is additional twinning evident in the Ten strong reflections uniformly distributed with regard to 20 (h0l) zeroJevel photograph, namely twinning by reflection on were measured at l0' intervals of Y (the azimuthal angle corre- {100}. Note that this twinning occurs for each member of the sponding to rotation of the crystal about its diffraction vector) plate {001} twin, resulting in four individual twin components. The rela- from O-350'. These data were used to calculate a thin em- tive amounts of the twin components were estimated as approxi- pirical absorption correction, the R (symmetric) index being re- mately 7O:25:4: I for the crystal used in the collection of the duced from 10.0% to 2.2% for the azimuthal data. This correction X-ray intensity data. was then applied to the whole data set, minimum and maximum The crystal was mounted on a Nicolet R3m automated four- transmission being 0.374 and 0.728 resepectively and the merging circle difractometer equipped with a molyMenum-target X-ray R (symmetric) being 2.3%. The data were also corrected for Lo- 0003{n4x/85/09l0-1050$02.00 1050 HAWTHORNE AND GROAT: STRUCTU RE OF WROEWOLFEIT E r051 Table 1. Miscellaneousinformation concerninswroewolfeite Structural description There is one unique S position in wroewolfeite;the S is a 6.045(l)R crystal size(m) O.O3x0.1zxo.l6 coordinatedby four 02- anions,the resulting tetrahedron b 5.646(l) RadlMono l'1olcr showing a typical range of bond lengthsand bond angles. c 14-337(2) Total lFoJ 1104 Thereare threelong S-O bonds,(S-O) :1.494, and one 6 93.39(l)o lrol '4 o 1008 short S-O bond, S-O : t.43A; this correlateswell with the V 488.5(l)R3 Non-overlappedlFol 7ll local bond-valencerequirements according to the hydrogen Space Group Pc Final R (obs) 6.7% bonding schemeproposed later. There are four unique Cu positions,each Cu being coordinatedby six anions in dis- Final Rw(obs) 6.2% torted octahedral arrangements.Cu(l) is coordinated by unit cell contents: 2[CuO(S0O)(0H)U'2Hrol one 02- and five (OH)t- anions,with four short meridio- - R = t(lFo-lFcl)/tlFol nal bonds and two longer axial bonds to one (OH)l and one O2-. Cu(2)is coordinatedby five (OH)- anionsand R" = [rw(lFo -lF. 12twr!]!, r=t one (HrO)' molecule, with four short meridional bonds and two longer axial bonds to an (OH)- and the (HzO)" molecule.Cu(3) and Cu(4) are both bonded to one 02- - anion and five (OH)l anions, again with similar distri- rcnl4 polaization and background effects, averaged and reduced butions of bond lengths.Thus eachof the Cu{u octahedra to structure factors. Of the 1104 unique reflections, 1008 were (where @: O2-, OH-, H2O) show typical Jahn-Teller classed as observed (l F"l < 4o). distortions involving strong extension of the axial Cu-f bonds. Solution and refinement The structure of wroewolfeiteis illustrated in Figures I Scatteringcurves for neutral atoms togetherwith anom- and 2. The fundamentalbuilding block (FBB) of the struc- alous dispersioncoefncients were taken from Cromer and ture (Hawthorne,1985a) is the [Cun(SOn[OH)rr]e- he- Mann (1968)and Cromer and Liberman (1970).R indices teropolyhedral cluster that is repeated by simple trans- are of the form given in Table I and are expressedas lation along a andb. This links, by octahedraledge-sharing percentages. in both directionsto form the structuremodule pictured in In the first stageof structuresolution, the overlap due to Figure 1, an infinite sheetof edge-sharingCu@, octahedra twinning was disregarded.The structure was solved by with projecting (SO4) tetrahedra; this has the formula direct methods.The distribution of E-valueswere charac- [Cuo(SOoXOH)r(HrO)]'.The structure module is elec- teristic of a non-centrosymmetricspace group, and thus the trostatically neutral, and adjacent sheetsare linked solely spacegroup Pc was adopted.The phaseset with the high- by hydrogen bonding, the proposed arrangement being est combinedfigure of merit gavea solution which eventu- shown in Figure 2. There is one unique (HrO) moleculein ally refined to an R index of -13%. The stereochemistry the structure that is not directlv bonded to a cation. How- of this model was rather nonsensical,and inspection of a differenceFourier map indicatedthe presenceof a twinned structure component.At this stage,reflections of the type Table 2. Atomic parametersfor wroewolfeite 4h. k. I were removedfrom the data set. A differenceFou- rier located the remaining anions, and subsequentrefine- y z u iso. ment convergedto an R index of 6.7% for an isotropic Cu(l) 0 0.3311(4) l/4 0.9r(5) thermal model. The diffraction data still containeda small cu(2) 0.5020(5) 0.3212(4) 0.250r(2) t.0t(5) contribution from the {001} twin, leading to overlap on Cu(3) -0.2476(5) -0.1682(4) 0.?428(21 1.02(5) ftlc0;however, removal of thesedata did not significantly cu(4) 0.2474(5) 0.1734(4) -0.2572(2) r 08(5) -0.07980r) affect the refinement results. Becauseof the incomplete s 0.0358(9) 0.035?(4) 1.43(8) o0 -0.0261(21 0.0098{27) 0.r376(9) r.4(3) data set (due to removalof partially overlapped ) ) reflections) 0(2) 0.1279125], 0.0012(30) -0.0132(r) 2.5{3) and residualeffects from other twin components.an aniso- 0( 3 ) -0.1607(24 ) 0.2811127 ) 0.0154(9) 1.8(3) tropic thermal model or refinementof H atom positions 0(4) -0.2443(?1) -0. l33l (33) 0.0052ilr ) 2.9(4) was not attempted.Final parametersare given in Table 2, 0(5)- 0.2525ile) 0.4991(2?l 0.r932(9) 0.8(2) observed and calculated structure factors are listed in o(6)r 0.2523(20) o-l4ol (23) 0.3052(8) 0.9(2) -0.?845123) Table 31 and interatomic distancesand anglesare given in 0{7)+ 0.0063(21) 0.3153(9) 0.9(2) 0.740609) 0.5073(2,]) 0.r894(9) 0.6(2) Table 4.
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